Pulping and Bleaching

PSE 476

Lecture #16
Sulfite Pulping

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 Sulfite Pulping
Agenda

• Conditions
• Cooking Liquor
» Preparation
• Factors Affecting Pulping
• Lignin Reactions
• Carbohydrate Reactions

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 Sulfite Pulping

• Unlike alkaline pulping, the purpose of sulfite

pulping is not heavy lignin fragmentation.
• Acid sulfite
» Under acidic conditions, the object is to solubilize lignin
through the addition of hydrophillic sulfonate groups
(sulfonation)
• Neutral sulfite
» Most often neutral sulfite pulping is used in association
with mechanical pulping (Neutral Sulfite Semi Chemical-
NSSC). The purpose here is mainly to “soften” the lignin.
• Alkaline sulfite
» The goal is sulfonation and fragmentation.

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 Sulfite Pulping
Conditions

Method pH “Base” Active Max Time @ Pulp Yield

Range Reagent Temp (°C) Temp (%)
(hrs)
2+ 2+ + -
Acid Long1-2
cookingCa
time,isMg , H
necessary , HSOdiffusion
to prevent 3 125-145
of SO2 ahead of 3-7 45-55
the base (avoid lignin
+ +
condensation,
Na , “black
NH4 cook”); weak pulp; low hemis; acid hydrolysis; tissue paper
2+ +
Bisulfite Medium
3-5 grades
Mgpaper: , H+and
, Nanewsprint , HSO -
writing
3 paper
150-170 1-3 50-65
+
NH4
+ + - 2-
Neutral 6-9stiffness
Good Napulp,
, NHhigh HSO
4 yield, 3 , SO3medium
corrugating 160-180 0.25-3 75-90
(NSSC)

Alkaline Very9-13
similar pulps
Na+ to kraft pulping
SOin 2-terms
, HOof- yield,160-180
brightness, bleachability
3-5 and strength
45-60
3

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 Sulfite Pulping
Sulfur Oxides Equilibriums

• Sulfur dioxide exists in different forms depending

upon solution pH. This is demonstrated by the
chemical equilibrium's shown below and in figure
in the next slide.

SO2 + H20 H2SO3 (SO2 . H20)

H2S03 + -
H + HSO3
- + -
HSO3 H + SO3

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 Effect of pH on Sulfur Dioxide
Species

100
% Sulfur Species

80
60 HSO3- SO32-
SO2
40
20
0
0 2 4 6 8 10
pH
Ca pH=2 to stay in the solution,
Mg pH=4,
Na and NH4+ strongly alkaline without precipitation (any pH).
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 Acid Sulfite Cooking Liquor
Production

• Molten sulfur is burned with O2 at

1100°C to form SO2
• Controlled regulation of O2 – over
oxidation production of SO3
• The SO2 is cooled to 200°C and
adsorbed into water forming SO2•
H2O often referred to as H2SO3
• A base is added to the SO2
» Ca, Na, NH3, Mg
• Liquor is fortified with additional
SO2 from digester (relief) in pressure
system
• Brow or a red liquor is the waste
liquor

Reference 7
 Sulfite Pulping
Variables
• Wood species
» Many softwoods (pines,etc) and hardwoods are difficult
to pulp particularly under acid conditions.
• General chip characteristics
» Size, Moisture, contaminants, etc.-very important to have
a uniform liquor penetration, if not chips will char not
enough base to supply the buffering action
• Cooking liquor
» Liquor/wood
• Digester variables
» Packing, venting, heating, etc.

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 Sulfite Pulping
Factors Affecting Cooking Rate

• pH, Rate 
• SO2 Concentration, Rate
• Temperature (most important), Rate 
• Base (from slowest to fastest)
» Ca<Na<Mg<NH4
» Other factors influence choice of base
- Costs: Mg>Na>NH4, Ca
- Recovery systems: calcium cannot typically be recovered
- NH4 pulps have lower brightness.

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 Sulfite Pulping
Lignin Reactions
At high temperatures a proton
attacks the benzylic oxygen Intermediate-
Three Major Reactions benzylic carbocation
CH3O CH3O CH3O
• Sulfonation HC O HC O HC O
HC O
.. R
» Sulfonation on a carbon
HC O R HC (+)
+ (+)
H H

(majority) and g carbon OCH3 OCH3 OCH3 + ROH

O (OH) O .. O
increases the polarity of (OH) (OH)

lignin and solubilize

lignin CH3O
CH3O

HC O
HC O
• Bond Cleavage*
-
HSO3 HC
HC SO3H

» Acid: a-O-4 linkage OCH

OCH 3
3

only linkage affected. O (OH)

O (OH)
(+)

» Neutral/Alkaline: b-O-
4, a-O-4 linkages * This reaction does not reduce MW or improve delignification
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cleaved.
 NSSC pulping

• Under neutral sulfite conditions:

» Sulfonation reactions are limited to β-O-4 ethers with free
phenolic hydroxyls only
» The net result of these reactions is light alpha-sulfonation
and some beta-ether cleavage
• Lignin is "softened" and most remains in the pulp
(higher temperatures it "gives" like thick molassas
and spreads out amongst the fibers)
• When made into a sheet and cooled down, the lignin
hardens again resulting in a stiff sheet
• This is the basis of cardboard type products

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 Sulfite Pulping
Lignin Reactions

• Condensation
» These reactions are very prevalent in acid sulfite pulping.
The MW of the lignin is significantly increased. This is a
detriment to lignin removal.
OCH3
(OH)
HC (+) HC O H HC O
(-)

OCH3
+
OCH3 OCH3
β-1
O O (+) O
(OH) R (OH) (OH)

HC (+) H HC

+ (-)
(+)
OCH3 β-6
OCH3 OCH3 O
OCH3 (OH)
O O O
(OH) (OH)
(OH)

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 Sulfite Pulping
Lignin Reactions ( What Really Happens)

• The unmentioned reaction.

» Six years ago it determined that there was basically
no free a-O-4 linkages in lignin. This means that the
proposed mechanisms for the reduction in lignin
molecular weight were incorrect.
» A forgotten proposed mechanism from Nakano
seems to explain this phenomena. In this
mechanism, lignin molecules are linked through
lignin-carbohydrate-lignin linkages. During acid
sulfite pulping, the carbohydrate is cleaved through
acid hydrolysis thus lowering the lignin molecular
weight.
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 Sulfite Pulping
Acid Reactions of Carbohydrates

• Cellulose: cleavage of glycosidic linkages slow because of

macromolecular structure: crystalline nature.
• Xylans:
» Arabinofuranosyl linkages very acid labile
» Uronic acid linkages somewhat stable
» Acetyl groups easily cleaved
• Galactoglucomannans:
 a-D-(1galactosidic linkage very acid labile
» Acetyl Groups easily cleaved; this increases
resistance of glucomannan linkages to cleavage
» Glucomannan linkages more stable than xylan

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 Sulfite Pulping
Acid Reactions of Carbohydrates

Cellulose Yield
100
Carbohydrate Yield %

80

60

40

20

0
40 45 50 55 60 65 70 75 80 85 90 95 100
Pulp Yield (%)

Carbohydrate degradation phenomena during sulfite cooking of Spruce

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 Softwood Xylans

4-b-D-Xly-14-b-D-Xly-14-b-D-Xly-14-b-D-Xly4-b-D-Xly
 




4-O-Me-a-D-Glc   
 a-L-Araf
2
2 2
OH OH
O O
HO O HO
O O
HO O O O
O O
O OH
OH
O
HO
H3CO
1 HO

COOH O
H
HO
OH

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HMFs and Furfurals

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 Sulfite Pulping
Reactions of Monosaccharides

• Monosaccharides react with bisulfite to form

aldonic acids under high temperature. Bisulfite is
converted to thiosulfate, thus severe lignin
condensation (black cook).
• In an acid sulfite cook, typically 10-20% of the
sugars are converted.
• Thiosulfate responsible for condensation reactions.
• Formation of thiosulfate is self catalyzing:
- -
RCHO + HSO3 RCOOH + S2O32 (Thiosulfate)
- - +
4 HS03 S2O32- +2 SO42 + 2H + H2O
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 Sulfite versus kraft

• Not used why:

1) New bleaching techniques made efficient bleaching
of kraft pulp possible
2) More pollution compared to kraft and high SO2 loss
to atmosphere
3) Applicable to small amount of wood species because
of limited capabilities to dissolve extractives (spruce,
balsam fir, and hemlock, aspen, poplar, birch, maple)
4) Long cooking process
5) Weaker pulp
6) Poor chemical recovery

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